Anomalous enhancement of negative sputtered ion emission by oxygen

Enhancement of negative sputtered ion yields by oxygen (either O⁺₂ bombardment or O₂ gas with Ar⁺ bombardment) is demonstrated for Si^?, As^?, P^?, Ga^?, Cu^? and Au^?, sputtered from a variety of matrices. Because oxygen also enhances positive ion yields of the same species, this effect cannot be simply explained on the basis of existing sputtered ion emission models. To rationalize these phenomena, a surface polarization model is developed which invokes localized electron emissive or electron retentive sites associated with differently oriented surface dipoles in the oxygenated surface. Such sites are considered to dominate the emission of negative and positive ions respectively. The model is shown to correctly predict that Au⁺ and Au^? ion yields are much more strongly enhanced by oxygen in dilute Au-Al alloys than in pure gold.     

Sputtering and secondary ion yields of metals subjected to oxygen ion bombardment

The yields of sputtering and secondary ion emission of metals under oxygen ion bombardment were simultaneously measured for multi-layer targets with known layer thickness. The sputtering yield of each layered metal was determined by the time to sputter away the thin film. The experimental results revealed that the sputtering yields of metals were reversely proportional to the energy transfer factor in the classical head-on collision model and a linear relationship was found between the ionization potential and a modified degree of ionization which can be expressed by the ionization potential and the secondary O⁺₂ current.     

Surface investigation of solids by the statical method of secondary ion mass spectroscopy (SIMS)

The physical and chemical properties of a solid surface are determined by its uppermost monolayers. Besides other methods like Auger electron spectroscopy (AES) and X-ray electron spectroscopy (ESCA) for example, the chemical composition of these uppermost monolayers can be investigated by the statical method of secondary ion mass spectroscopy (SIMS). In this method a relatively large target area (0.1 cm²) is bombarded with a small primary ion current density (10^?9 A cm^?2). Thus a sputtering time of several hours is achieved for an individual monolayer. A mass analysis of the emitted positive and negative secondary ions gives information about the chemical composition of the uppermost monomolecular layer of the bombarded surface. Important features of SIMS are: detection of chemical compounds; isotope sensitivity; detection of hydrogen and its compounds ; depth resolution in the range of a single monolayer ; low detection limits (< 10^?6 monolayer or < 10^?14 g) for many elements and compounds.The capacity of this method is demonstrated using as examples the initial surface oxidation of metals and semiconductors and adsorption phenomena on clean metal surfaces. In some special cases additional information on the chemical composition of the uppermost monolayer can be obtained by the electron induced ion emission from the surface.     

Determination of the negative ion yield of copper sputtered by cesium ions

Abstract

This paper describes the determination of secondary ion yields for negative ions obtained by bombardment of copper by cesium ions. Stable and reproducible surface conditions are reached by high rate sodium deposition simultaneously with sputtering. An optimum thickness of sodium corresponding to about one monolayer is found. Total negative ion yields K ^? _Σ are measured by a double modulation technique. Individual negative ion yields K ^? _i are then found by mass spectrometrically determining the various negative ion intensities, the sum of which relates linearly to K ^? _Σ. This method is based on the assumption of an equal angular and energy distribution of all sputtered negative ions. Data are given for K^? _Σ and K ^? _Cu and K^? _O. The dependence of K ^? _i on primary ion energy (500 to 2500 eV) is similar to ordinary sputtering which points to the same basic mechanism in both cases.     

Sputtering of highly oriented pyrolytic graphite with 30 keV Argon ions

The influence of the incidence angle of 30 keV Ar⁺ ions, ion fluence and target temperature on the sputtering yield and surface microgeometry of highly oriented pyrolytic graphite (UPV-1T) samples was experimentally studied. It was found that at fluences more than 5 × 10¹⁹ ion cm^?2 the sputtering yield at room temperature in the range of the ion incidence angle from 0° to 80° is twice as small as the corresponding experimental data for both polycrystalline graphite and glassy carbon. The analysis of ion-induced relief permits us to suppose the topographical suppression mechanism of highly oriented pyrolytic graphite sputtering.     

Propagation and Diagnostic of Ion Acoustic Waves in a Low Pressure Argon Discharge

In a dc argon discharge column of pressure 5 × 10^?4 torr, ion acoustic waves are studied experimentally. Plasma parameters obtained from the phase velocity of waves are compared with the Langmuir probe measurements. The wave diagnostic method yields the electron temperature lower than the probe method by a factor of 3…?5, if the atomic argon ion is assumed as a dominant ion species. The axial profiles of ion drift velocity show the presence of ions flowing toward the anode along the potential drop in flont of it. Also it is found that the surface condition of the cathode sensitively affects the propagation of ion acoustic waves through the changes in discharge parameters.     

Mass spectrometry of molecular neutrals sputtered from amino acid overlayers on Au and Ni

Mass spectrometry of electron post-ionized sputtered neutrals (e-beam SNMS) is a useful new surface mass spectrometry, complementary to secondary ion (SIMS) and thermal desorption (TDMS) mass spectrometry. This is demonstrated by applying these three techniques to identical mono- and multimolecular overlayers of glycine on the metal (Me) substrates Ni and Au. In particular the molecular neutrals M⁰ and (M + Me)^o supply new information about the sputtering process, and show the analytical potential of e-beam SNMS for quantitative molecular surface analysis.     

Ion sputtering of minerals and glasses: a first step to the simulation of solar wind erosion

Selected rockforming minerals (plagioclase, augite, olivine, ilmenite, silicate and metal phases of the meteorite “Brenham”) as well as silicate and phosphate glasses were irradiated with heavy ions (⁴He⁺, ¹⁴N+, ²⁰Ne⁺, ⁴⁰Ar+, ⁵⁶Fe+, Xe⁺ _nat) in the energy range of 50-130 keV in order to study ion-induced sputtering. Sputtering yields were measured independently by means of multiple beam interferometry and particle track autoradiography.

The theory of sputtering by Sigmund, modified by Smith, was used to convert experimental heavy ion sputtering yields to H⁺- and He⁺-sputtering yields of the same target. Taking into account solar wind irradiation conditions at the lunar surface, an estimate of lunar erosion rates due to solar wind sputtering is given for the targets studied.     

Sputtering of Cu and Zn atoms from elemental and alloy targets

The energy distributions of Cu and Zn atoms sputtered from elements and Cu_xZn_1-x alloys (x=0.80, 0.24) with a 6 keV Ar⁺ beam have been measured. It was found that the collision-cascade theory properly described the flux of sputtered atoms. From the spectra the binding energies of Cu and Zn atoms in the elemental and alloy surfaces were determined. The collision-cascade theory and the experimentally adjusted values of the binding energies allowed for calculation of the total and partial sputtering yields, and the equilibrium surface composition of the ion bombarded alloys. This work was carried out as a part of Research Project M.R. I/5.     

Ion sputtering rates of W-, Ti- and Cr-carbides studied at different Ar ion incidence angles

To study the ion sputtering rates of W-, Ti- and Cr-carbides, trilayer structures comprising C-graphite (59 nm)/WC (50 nm)/W (38 nm), C-graphite (56 nm)/TiC (40 nm)/Ti (34 nm) and C-graphite (46 nm)/C₃C₂ (60 nm)/Cr (69 nm) with a tolerance ±2% were sputter deposited onto smooth silicon substrates. Their precise structural and compositional characterization by transmission electron microscopy (TEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) revealed that the WC and Cr₃C₂ layers were amorphous, while the TiC layer had a polycrystalline structure. The ion sputtering rates of all three carbides, amorphous carbon and polycrystalline Cr, Ti and W layers were determined by means of Auger electron spectroscopy depth profiling as a function of the angle of incidence of two symmetrically inclined 1 keV Ar⁺ ion beams in the range between 22° and 82°. The sputtering rates were calculated from the known thicknesses of the layers and the sputtering times necessary to remove the individual layers. It was found that the sputtering rates of carbides, C-graphite and metals were strongly angle dependent. For the carbides in the range between 36° and 62° the highest ion sputtering rate was found for Cr₃C₂ and the lowest for TiC, while the values of the sputtering rates for WC were intermediate. The normalized sputtering yields calculated from the experimentally obtained data for all three carbides followed the trend of theoretical results obtained by calculation of the transport of ions in solids by the SRIM code. The sputtering yields are also presented in terms of atoms/ion. Our experimental data for two ion incidence angles of 22° and 49° and reported values of other authors for C-graphite and metals are mainly inside the estimated error of about ±20%. The influence of the ion-induced surface topography on the measured sputtering yields was estimated from the atomic force microscope (AFM) measurements at the intermediate points of the corresponding layers on the crater walls formed during depth profiling.     

Langmuir Probe Diagnostics of a Low Temperature Non-Isothermal Plasma in a Weak Magnetic Field

This article presents measurements by a cylindrical Langmuir probe in the plasma of a DC cylindrical magnetron discharge át the pressure 1.5 Pa that aim at the experimental assessment of the influence of a weak magnetic field to the estimation of the electron density when using conventional methods of probe data interpretation. The probe data was obtained under the presence of a weak magnetic field in the range 1.10^?2?5.10^?2 T. The influence of the magnetic field on the electron probe current is experimentally assessed for two cylindrical probes with different radii, 50 μm and 21 μm. This assessment is based on comparison of the values of the electron density estimated from the electron current part with the values of the positive ion density estimated from the positive ion current part of the probe characteristic respectively by assuming that at the magnetic field strengths used in the present study the probe positive ion currents are possible to be assumed as uninfluenced by the magnetic field. For interpretation of the probe positive ion current two theories are used and compared to each other: the radial motion model by Allen, Boyd and Reynolds [10] and Chen [11] and the model that accounts for the collisions of positive ions with neutrals in the probe space charge sheath that we call Chen-Talbot model [8]. At lower magnetic field 3 · 10^?2 T the positive ion density values interpreted by using the Chen-Talbot model [8] are in better agreement with the values of electron density compared to those obtained by using the theory [10,11]; therefore the model [8] is used for calculation of the positive ion density from the probe data at higher magnetic fields. The comparison of the positive ion and electron density values calculated from the same probe data at higher magnetic fields shows that up to the magnetic field strength 4 . 10^?2 T with the probe 100 μm and up to 5 . 10^?2 T with the probe 42 μm in diameter respectively the decrease of the magnitude of the electron current at the space potential due to the magnetic field does not exceed the error limits that are usual for Langmuir probe measurements (absolute error ±20%).     

Investigation on surface compositions of CuNi alloy under Ar+ ion bombardment by ISS and in situ AES measurements

Surface compositions of CuNi(50 wt%) alloy under 3 keV Ar⁺ ion bombardment were measured by Auger electron spectroscopy (AES) and ion scattering spectroscopy (ISS). In situ AES measurement of sputter-deposited layer and sputtered sample surface indicated that surface composition became Ni-rich due to Ar⁺ ion sputtering at steady state, in accord with previous reports of preferential sputtering. ISS measurements with 3 keV Ar⁺ ions, however, have suggested that the composition of the outermost atom layer is not Ni-rich but slightly copperrich. This leads to the conclusion that the degree of preferential sputtering is small and that the question of preferential sputtering, particularly, the ratio of the sputtering yields, $\text{S}{}_{\mathrm{<mtext>Cu</mtext>}}\text{S}{}_{\mathrm{<mtext>Ni</mtext>}}$, based on AES measurement requires further examination.     

Modelling ion-assisted deposition of CeO2 films

The theory presented explains quantitatively the experimentally observed increase in film density of a vapor-deposited CeO₂ film when bombarded during growth with low-energy O ₂ ⁺ ions. The density enhancement is expressed in terms of the yields for recoil implantation of surface atoms, ion incorporation and sputtering, which have been determined by employing a three-dimensional Monte Carlo cascade calculation. Ion-to-vapor flux ratios between 0 and 1.4 and O⁺ ion energies between 25 and 600 eV have been examined. The density shows an almost linear increase with the ratio of ion-to-vapor fluxes. An optimum O⁺ ion energy for densification is found at about 200 eV which is in agreement with experiment.     

Electron microprobe compositional analysis of sputtered tantalum-aluminium films

In the present paper the methods for measurement of the composition of two or more component tantalum-based thin sputtered films are summarized. The influence of the target construction on the composition of the films is discussed. The Ta-Al films were sputtered from composite Ta-Al targets. The composition of films was measured by means of the electron microprobe technique. From results it follows that using the composite targets for sputtering in argon at a pressure of 2×10^?2 torr and in its mixture with nitrogen (10^?3 torr), the composition of Ta-Al films is proportional to the ratio of the Ta and Al exposed surfaces on the target. The proportionality factor equals to the ratio of “effective” sputtering yields of target components measured at given sputtering conditions. The presence of nitrogen in sputtering gas decreases the value of Ta yield 2.2 times. If a small Al surface is sputtered together with much larger Ta surface, the sputtering yield of Al remains unchanged. In Ta-Al films the occluded argon was qualitatively determined. The presence of nitrogen was not proved. This seems to be caused by the absorption of nitrogen characteristic radiation in the investigated films.     

Carbon sputtering yield measurements at grazing incidence

In this investigation, carbon sputtering yields were measured experimentally at varying angles of incidence under Xe⁺ bombardment. The measurements were obtained by etching a coated quartz crystal microbalance (QCM) with a low energy ion beam. The material properties of the carbon targets were characterized with a scanning electron microscope (SEM) and Raman spectroscopy. C sputtering yields measured under Ar⁺ and Xe⁺ bombardment at normal incidence displayed satisfactory agreement with previously published data over an energy range of 200 eV-1 keV. For Xe⁺ ions, the dependence of the yields on angle of incidence θ was determined for 0° ≤ θ ≤ 80°. Over this range, an increase in C sputtering yield by a factor of 4.8 was observed, with the peak in yield occurring at 70°. This is a much higher variation compared to Xe⁺ → Mo yields under similar conditions, a difference that may be attributed to higher scattering of the incident particles transverse to the beam direction than in the case of Xe⁺ → C. In addition, the variation of the yields with θ was not strongly energy dependent. Trapping of Xe in the surface was observed, in contrast to observations using the QCM technique with metallic target materials. Finally, target surface roughness was characterized using atomic force microscope measurements to distinguish between the effects of local and overall angle of incidence of the target.     

Die Analyse monomolekularer FestkörperoberflÄchenschichten mit Hilfe der SekundÄrionenemission

The use of extremely low primary ion current densities (10^?9 A cm^?2) increases the sputtering time of the original first monolayer of a solid to such a degree (>10⁴ s), that the analysis of this layer by secondary ion spectroscopy can be realized. Changes in its composition (caused by surface reactions, particle bombardment etc.) can be observed for a long period before a considerable fraction of the surface has interacted with the weak ion beam. The capacity of the method is demonstrated by analysis results of Ag and Mo surfaces. Many kinds of ions follow exactly the time dependenceN(t)=N(0)e ^?t/T, characteristic exclusively for ions originating from components present only in the first monolayer. The detection limit for several complex anions is below 1 ppm of a monolayer (<10^?15 g). This method of monolayer analysis shows some advantages compared with electron probe x-ray analysis or Auger electron spectroscopy: Isotope separation, detection of changes of concentration within the first few monolayers, and especially the detection of chemical compounds.     

Sputtering of Ta2O5 by Ar+ ions at energies below 1 keV

The sputtering of anodically formed Ta₂O₅ layers of about 3500 Å thickness has been studied by Sputtered Neutral Mass Spectroscopy (SNMS). For perpendicular bombardment with Ar⁺ ions up to 900 eV the flux of ejected neutral particles is found to consist almost exclusively of metal atoms Ta and Oxide specific molecules TaO and TaO₂ with intensity ratios in the order 1 : 1 : 10^?1. From depth profiling measurements with SNMS, and from the intensity ratios in the SNMS spectra the total sputtering yield of Ta₂O₅ and the partial yields of Ta, TaO and of oxygen have been determined for normally incident Ar⁺ ions of 100 to 600 eV. After an initial increase the TaO intensity in the SNMS spectra remains constant during the sputter removal of the whole layer. A simple model is derived by which the preferred emission of TaO molecules, and the initial increase of the TaO intensity is referred to ion induced variations of the surface stoichiometry of Ta₂O₅. For optimum TaO production the model predicts equal atomic surface concentrations of Ta and O.     

Sputtering-induced nanometre hole formation in Ni3Al under intense electron beam irradiation

The irradiation damage of polycrystalline Ni₃Al thin foils of stoichiometric composition by a stationary nanoscale 200?keV field emission gun (FEG) electron probe in a FEI Tecnai F20 (S)TEM has been investigated. At current densities greater than 10⁷?A/m², nanometre holes are produced quickly with both ?001? and ?110? incident electron beam directions. EDX spectra from the irradiated volume have been collected simultaneously during the hole forming process. From the EDX results, preferential surface sputtering of aluminium from Ni₃Al has been demonstrated. To understand the underlying physical process of sputtering, modelling based on a combination of molecular dynamics and Monte Carlo simulation has been performed. It appears to reproduce faithfully the overall film sputtering and hole formation processes, but is not capable of predicting the detailed geometry of the hole. It predicts that the sputtering cross-section of Al atoms is much higher than that of Ni atoms, resulting in a very small concentration of Al at the surface. This, together with the increase of surface area during hole formation, explains the preferential Al loss observed from the specimen. Calculated sputtering rates agree well with experiment, and are of the order of magnitude of 10^?8?atoms/electron.     

Initial electron back-scattered diffraction observations of cerium

The first electron back-scattered diffraction Kikuchi patterns and grain orientation maps were captured for pure n-phase (fcc) Ce. The sample preparation technique used for electron back-scattered diffraction orientation mapping of this surface-reactive metal included ion sputtering the surface using a scanning Auger microprobe followed by vacuum transfer of the sample from the scanning Auger microprobe to the scanning electron microscope. The effect of ion sputtering on the microstructure as well as preliminary electron back-scattered diffraction microstructural characterization is presented. Based on the sputtering data, the room-temperature diffusivity of O in n-Ce was estimated.     

Effect of surface steps on sputtering and surface defect formation: molecular-dynamics study of 5 keV Xe bombardment of Pt(1 1 1) at glancing incidence angles

Using molecular-dynamics simulation, we study sputtering and defect formation induced by 5 keV Xe⁺ ion impact on a Pt(1 1 1) surface at oblique and glancing incidence angles. Impact on a terrace produces yield maxima at ?=60-65° incidence angle towards the surface normal. Beyond 75-80°, no damage is produced due to projectile ion reflection. Impact on a dense-packed step, however, produces defects in sizeable numbers up to glancing incidence, ?=85°. The dependence of the yields on the incidence angle and distance of the impact point of the projectile to the step are discussed.